Microwave Doping of Sulfur and Iron in ß12 Borophene.

Borophene, a 2D material exhibiting unique crystallographic phases like the anisotropic atomic lattices of ß12 and X3 phases, has attracted considerable attention due to its intriguing Dirac nature and metallic attributes. Despite surpassing graphene in electronic mobility, borophene's potential in energy storage and catalysis remains untapped due to its inherent electrochemical and catalytic limitations. Elemental doping emerges as a promising strategy to introduce charge carriers, enabling localized electrochemical and catalytic functionalities. However, effective doping of borophene has been a complex and underexplored challenge. Here, an innovative, one-pot microwave-assisted doping method, tailored for the ß12 phase of borophene is introduced. By subjecting dispersed ß12 borophene in dimethylformamide to controlled microwave exposure with sulfur powder and FeCl3 as doping precursors, S- and Fe doping in borophene can be controlled. Employing advanced techniques including high-resolution transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, confirm successful sulfur and iron dopant incorporation onto ß12 borophene is confirmed, achieving doping levels of up to 11 % and 13 %, respectively. Remarkably, S- and Fe-doped borophene exhibit exceptional supercapacitive behavior, with specific capacitances of 202 and 120 F g-1 , respectively, at a moderate current density of 0.25 A g-1 .

Bridging Together Theoretical and Experimental Perspectives in Single-Atom Alloys for Electrochemical Ammonia Production.

Ammonia is an essential commodity in the food and chemical industry. Despite the energy-intensive nature, the Haber-Bosch process is the only player in ammonia production at large scales. Developing other strategies is highly desirable, as sustainable and decentralized ammonia production is crucial. Electrochemical ammonia production by directly reducing nitrogen and nitrogen-based moieties powered by renewable energy sources holds great potential. However, low ammonia production and selectivity rates hamper its utilization as a large-scale ammonia production process. Creating effective and selective catalysts for the electrochemical generation of ammonia is critical for long-term nitrogen fixation. Single-atom alloys (SAAs) have become a new class of materials with distinctive features that may be able to solve some of the problems with conventional heterogeneous catalysts. The design and optimization of SAAs for electrochemical ammonia generation have recently been significantly advanced. This comprehensive review discusses these advancements from theoretical and experimental research perspectives, offering a fundamental understanding of the development of SAAs for ammonia production.

Charge transfer in TiO2-based photocatalysis: fundamental mechanisms to material strategies.

Semiconductor-based photocatalysis has attracted significant interest due to its capacity to directly exploit solar energy and generate solar fuels, including water splitting, CO2 reduction, pollutant degradation, and bacterial inactivation. However, achieving the maximum efficiency in photocatalytic processes remains a challenge owing to the speedy recombination of electron-hole pairs and the limited use of light. Therefore, significant endeavours have been devoted to addressing these issues. Specifically, well-designed heterojunction photocatalysts have been demonstrated to exhibit enhanced photocatalytic activity through the physical distancing of electron-hole pairs generated during the photocatalytic process. In this review, we provide a systematic discussion ranging from fundamental mechanisms to material strategies, focusing on TiO2-based heterojunction photocatalysts. Current efforts are focused on developing heterojunction photocatalysts based on TiO2 for a variety of photocatalytic applications, and these projects are explained and assessed. Finally, we offer a concise summary of the main insights and challenges in the utilization of TiO2-based heterojunction photocatalysts for photocatalysis. We expect that this review will serve as a valuable resource to improve the efficiency of TiO2-based heterojunctions for energy generation and environmental remediation.

Nanohybrids of BCN-Fe1-x S for Sodium and Lithium Hybrid Ion Capacitors.

Hybrid ion capacitors (HIC) are receiving a lot of attention due to their potential to achieve high energy and power densities, but they remain insufficient. It is imperative to explore outstanding and environmentally benign electrode materials to achieve high-performing HIC systems. Here, a unique boron carbon nitride (BCN)-based HIC system that comprises a microporous BCN structure and Fe1-x S nanoparticle incorporated BCN nanosheets (BNF) as cathode and anode, respectively is reported. The BNF is prepared through a facile one-pot calcination process using dithiooxamide (DTO), boric acid, and iron source. In situ, crystal growth of Fe1-x S facilitates the formation of BCN structure through the creation of holes/defects in the polymeric structure. The first principle density functional (DFT) theory simulations demonstrate the structural and electronic properties of the hybrid of BCN and Fe1-x S as compelling anode materials for HIC applications. The DFT calculations reveal that both BCN and BNF structures have excellent metallic characters with Li+ storage capacities of 128.4 and 1021.38 mAh g-1  respectively. These findings are confirmed experimentally where the BCN-based HIC system delivers exceptional energy and power densities of 267.5 Wh kg-1 /749.5 W kg-1 toward Li+ storage, which outweighs previous HIC performances and demonstrates favorable performance for Li+ and Na+ storages.

Bio-Inspired Supramolecular Self-Assembled Carbon Nitride Nanostructures for Photocatalytic Water Splitting.

Fast production of hydrogen and oxygen in large amounts at an economic rate is the need of the hour to cater to the needs of the most awaited hydrogen energy, a futuristic renewable energy solution. Production of hydrogen through simple water splitting via visible light photocatalytic approach using sunlight is considered as one of the most promising and sustainable approaches for generating clean fuels. For this purpose, a variety of catalytic techniques and novel catalysts have been investigated. Among these catalysts, carbon nitride is presently deemed as one of the best candidates for the visible light photocatalysis due to its unique molecular structure and adequate visible-range bandgap. Its bandgap can be further engineered by structural and morphological manipulation or by doping/hybridization. Among numerous synthetic approaches for carbon nitrides, supramolecular self-assembly is one of the recently developed elegant bottom-up strategies as it is bio-inspired and provides a facile and eco-friendly route to synthesize high surface area carbon nitride with superior morphological features and other semiconducting and catalytic properties. The current review article broadly covers supramolecular self-assembly synthesis of carbon nitride nanostructures and their photocatalytic water-splitting applications and provides a comprehensive outlook on future directions.

Biochar modulating soil biological health: A review.

Biochar can be used for multifunctional applications including the improvement of soil health and carbon storage, remediation of contaminated soil and water resources, mitigation of greenhouse gas emissions and odorous compounds, and feed supplementation to improve animal health. A healthy soil preserves microbial biodiversity that is effective in supressing plant pathogens and pests, recycling nutrients for plant growth, promoting positive symbiotic associations with plant roots, improving soil structure to supply water and nutrients, and ultimately enhancing soil productivity and plant growth. As a soil amendment, biochar assures soil biological health through different processes. First, biochar supports habitats for microorganisms due to its porous nature and by promoting the formation of stable soil micro-aggregates. Biochar also serves as a carbon and nutrient source. Biochar alters soil physical and chemical properties, creating optimum soil conditions for microbial diversity. Biochar can also immobilize soil pollutants and reduce their bioavailability that would otherwise inhibit microbial growth. However, depending on the pyrolysis settings and feedstock resources, biochar can be comprised of contaminants including polycyclic aromatic hydrocarbons and potentially toxic elements that can inhibit microbial activity, thereby impacting soil health.

Incorporation of Bimetallic Sulfide with Carbon Nitride for Advanced Na-Ion Batteries.

Sodium-ion batteries (SIBs) have received tremendous attention owing to their low cost, high working voltages, and energy density. However, the design and development of highly efficient SIBs represent a great challenge. Here, a unique and reliable approach is reported to prepare carbon nitride (CN) hybridized with nickel iron sulfide (NFCN) using simple reaction between Ni-Fe layered double hydroxide and dithiooxamide. The characterization results demonstrate that the hybridization with optimal amount of CN induces local distortion in the crystal structure of the hybrid, which would benefit SIB performance. Systematic electrochemical studies with a half-cell configuration show that the present hybrid structure exhibits a promising reversible specific capacity of 348 mAh g-1 at 0.1 A g-1 after 100 cycles with good rate capability. Simulation result reveals that the iron atoms in nickel iron sulfide act as a primary active site to accommodate Na+ ions. At last, with a full cell configuration using NFCN and Na3 V2 (PO4 )2 O2 F as the anode and cathode, respectively, the specific capacity appears to be ≈95 mAh g-1 after 50 cycles at 0.1 A g-1 condition. This excellent performance of these hybrids can be attributed to the synergistic effect of the incorporated CN species and the high conductivity of nickel-iron sulfide.

Natural Products Derived Porous Carbons for CO2 Capture.

As it is now established that global warming and climate change are a reality, international investments are pouring in and rightfully so for climate change mitigation. Carbon capture and separation (CCS) is therefore gaining paramount importance as it is considered one of the powerful solutions for global warming. Sorption on porous materials is a promising alternative to traditional carbon dioxide (CO2 ) capture technologies. Owing to their sustainable availability, economic viability, and important recyclability, natural products-derived porous carbons have emerged as favorable and competitive materials for CO2 sorption. Furthermore, the fabrication of high-quality value-added functional porous carbon-based materials using renewable precursors and waste materials is an environmentally friendly approach. This review provides crucial insights and analyses to enhance the understanding of the application of porous carbons in CO2 capture. Various methods for the synthesis of porous carbon, their structural characterization, and parameters that influence their sorption properties are discussed. The review also delves into the utilization of molecular dynamics (MD), Monte Carlo (MC), density functional theory (DFT), and machine learning techniques for simulating adsorption and validating experimental results. Lastly, the review provides future outlook and research directions for progressing the use of natural products-derived porous carbons for CO2 capture.

Multifunctional carbon nitride nanoarchitectures for catalysis.

Catalysis is at the heart of modern-day chemical and pharmaceutical industries, and there is an urgent demand to develop metal-free, high surface area, and efficient catalysts in a scalable, reproducible and economic manner. Amongst the ever-expanding two-dimensional materials family, carbon nitride (CN) has emerged as the most researched material for catalytic applications due to its unique molecular structure with tunable visible range band gap, surface defects, basic sites, and nitrogen functionalities. These properties also endow it with anchoring capability with a large number of catalytically active sites and provide opportunities for doping, hybridization, sensitization, etc. To make considerable progress in the use of CN as a highly effective catalyst for various applications, it is critical to have an in-depth understanding of its synthesis, structure and surface sites. The present review provides an overview of the recent advances in synthetic approaches of CN, its physicochemical properties, and band gap engineering, with a focus on its exclusive usage in a variety of catalytic reactions, including hydrogen evolution reactions, overall water splitting, water oxidation, CO2 reduction, nitrogen reduction reactions, pollutant degradation, and organocatalysis. While the structural design and band gap engineering of catalysts are elaborated, the surface chemistry is dealt with in detail to demonstrate efficient catalytic performances. Burning challenges in catalytic design and future outlook are elucidated.

Realization of High Magnetization in Artificially Designed Ni/NiO Layers through Exchange Coupling.

High-magnetization materials play crucial roles in various applications. However, the past few decades have witnessed a stagnation in the discovery of new materials with high magnetization. In this work, Ni/NiO nanocomposites are fabricated by depositing Ni and NiO thin layers alternately, followed by annealing at specific temperatures. Both the as-deposited samples and those annealed at 373 K exhibit low magnetization. However, the samples annealed at 473 K exhibit a significantly enhanced saturation magnetization exceeding 607 emu cm-3 at room temperature, surpassing that of pure Ni (480 emu cm-3 ). Material characterizations indicate that the composite comprises NiO nanoclusters of size 1-2 nm embedded in the Ni matrix. This nanoclustered NiO is primarily responsible for the high magnetization, as confirmed by density functional theory calculations. The calculations also indicate that the NiO clusters are ferromagnetically coupled with Ni, resulting in enhanced magnetization. This work demonstrates a new route toward developing artificial high-magnetization materials using the high magnetic moments of nanoclustered antiferromagnetic materials.

Utilising the Nanozymatic Activity of Copper-Functionalised Mesoporous C3 N5 for Sensing Biomolecules.

Designing unique nanomaterials for the selective sensing of biomolecules is of significant interest in the field of nanobiotechnology. In this work, we demonstrated the synthesis of ordered Cu nanoparticle-functionalised mesoporous C3 N5 that has unique peroxidase-like nanozymatic activity for the ultrasensitive and selective detection of glucose and glutathione. A nano hard-templating technique together with the in-situ polymerisation and self-assembly of Cu and high N-containing CN precursor was adopted to introduce mesoporosity as well as high N and Cu content in mesoporous C3 N5 . Due to the ordered structure and highly dispersed Cu in the mesoporous C3 N5 , a large enhancement of the peroxidase mimetic activity in the oxidation of a redox dye in the presence of hydrogen peroxide could be obtained. Additionally, the optimised Cu-functionalised mesoporous C3 N5 exhibited excellent sensitivity to glutathione with a low detection limit of 2.0 ppm. The strong peroxidase activity of the Cu-functionalised mesoporous C3 N5 was also effectively used for the sensing of glucose with a detection limit of 0.4 mM through glucose oxidation with glucose oxidase. This unique Cu-functionalised mesoporous C3 N5 has the potential for detecting various molecules in the environment as well as for next-generation glucose and glutathione diagnostic devices.

Strategies for Improving the Photocatalytic Hydrogen Evolution Reaction of Carbon Nitride-Based Catalysts.

Due to the depletion of fossil fuels and their-related environmental issues, sustainable, clean, and renewable energy is urgently needed to replace fossil fuel as the primary energy resource. Hydrogen is considered as one of the cleanest energies. Among the approaches to hydrogen production, photocatalysis is the most sustainable and renewable solar energy technique. Considering the low cost of fabrication, earth abundance, appropriate bandgap, and high performance, carbon nitride has attracted extensive attention as the catalyst for photocatalytic hydrogen production in the last two decades. In this review, the carbon nitride-based photocatalytic hydrogen production system, including the catalytic mechanism and the strategies for improving the photocatalytic performance is discussed. According to the photocatalytic processes, the strengthened mechanism of carbon nitride-based catalysts is particularly described in terms of boosting the excitation of electrons and holes, suppressing carriers recombination, and enhancing the utilization efficiency of photon-excited electron-hole. Finally, the current trends related to the screening design of superior photocatalytic hydrogen production systems are outlined, and the development direction of carbon nitride for hydrogen production is clarified.

Design and Synthesis of Cabazitaxel Loaded Core-Shell Mesoporous Silica Nanoparticles with Different Morphologies for Prostate Cancer Therapy.

In this work, the synthesis of core-shell ordered mesoporous silica nanoparticles (CSMS) with tunable particle size and shape through a dual surfactant-assisted approach is demonstrated. By varying the synthesis conditions, including the type of the solvent and the concentration of the surfactant, monodispersed and ordered mesoporous silica nanoparticles with tunable particle size (140-600 nm) and morphologies (hexagonal prism (HP), oblong, spherical, and hollow-core) can be realized. Comparative studies of the Cabazitaxel (CBZ)-loaded HP and spherical-shaped CSMS are conducted to evaluate their drug delivery efficiency to PC3 (prostate cancer) cell lines. These nanoparticles showed good biocompatibility and displayed a faster drug release at acidic pH than at basic pH. The cellular uptake of CSMS measured using confocal microscopy, flow cytometry, microplate reader, and ICP-MS (inductively coupled plasma mass spectrometry) techniques in PC3 cell lines revealed a better uptake of CSMS with HP morphology than its spherical counterparts. Cytotoxicity study showed that the anticancer activity of CBZ is improved with a higher free radical production when loaded onto CSMS. These unique materials with tunable morphology can serve as an excellent drug delivery system and will have potential applications for treating various cancers.

Organocatalysis with carbon nitrides.

Carbon nitrides, a distinguished class of metal-free catalytic materials, have presented a good potential for chemical transformations and are expected to become prominent materials for organocatalysis. This is largely possible due to their low cost, exceptional thermal and chemical stability, non-toxicity, ease of functionalization, porosity development, etc. Especially, the carbon nitrides with increased porosity and nitrogen contents are more versatile than their bulk counterparts for catalysis. These N-rich carbon nitrides are discussed in the earlier parts of the review. Later, the review highlights the role of such carbon nitride materials for the various organic catalytic reactions including Knoevenagel condensation, oxidation, hydrogenation, esterification, transesterification, cycloaddition, and hydrolysis. The recently emerging concepts in carbon nitride-based organocatalysis have been given special attention. In each of the sections, the structure-property relationship of the materials was discussed and related to their catalysis action. Relevant comparisons with other catalytic materials are also discussed to realize their real potential value. The perspective, challenges, and future directions are also discussed. The overall objective of this review is to provide up-to-date information on new developments in carbon nitride-based organic catalysis reactions that could see them rising as prominent catalytic materials in the future.

Recent Advances in Carbon-Based Electrodes for Energy Storage and Conversion.

Carbon-based nanomaterials, including graphene, fullerenes, and carbon nanotubes, are attracting significant attention as promising materials for next-generation energy storage and conversion applications. They possess unique physicochemical properties, such as structural stability and flexibility, high porosity, and tunable physicochemical features, which render them well suited in these hot research fields. Technological advances at atomic and electronic levels are crucial for developing more efficient and durable devices. This comprehensive review provides a state-of-the-art overview of these advanced carbon-based nanomaterials for various energy storage and conversion applications, focusing on supercapacitors, lithium as well as sodium-ion batteries, and hydrogen evolution reactions. Particular emphasis is placed on the strategies employed to enhance performance through nonmetallic elemental doping of N, B, S, and P in either individual doping or codoping, as well as structural modifications such as the creation of defect sites, edge functionalization, and inter-layer distance manipulation, aiming to provide the general guidelines for designing these devices by the above approaches to achieve optimal performance. Furthermore, this review delves into the challenges and future prospects for the advancement of carbon-based electrodes in energy storage and conversion.

Stimuli-Responsive Silica Silanol Conjugates: Strategic Nanoarchitectonics in Targeted Drug Delivery.

The design of novel drug delivery systems is exceptionally critical in disease treatments. Among the existing drug delivery systems, mesoporous silica nanoparticles (MSNs) have shown profuse promise owing to their structural stability, tunable morphologies/sizes, and ability to load different payload chemistry. Significantly, the presence of surface silanol groups enables functionalization with relevant drugs, imaging, and targeting agents, promoting their utility and popularity among researchers. Stimuli-responsive silanol conjugates have been developed as a novel, more effective way to conjugate, deliver, and release therapeutic drugs on demand and precisely to the selected location. Therefore, it is urgent to summarize the current understanding and the surface silanols' role in making MSN a versatile drug delivery platform. This review provides an analytical understanding of the surface silanols, chemistry, identification methods, and their property-performance correlation. The chemistry involved in converting surface silanols to a stimuli-responsive silica delivery system by endogenous/exogenous stimuli, including pH, redox potential, temperature, and hypoxia, is discussed in depth. Different chemistries for converting surface silanols to stimuli-responsive bonds are discussed in the context of drug delivery. The critical discussion is culminated by outlining the challenges in identifying silanols' role and overcoming the limitations in synthesizing stimuli-responsive mesoporous silica-based drug delivery systems.

Borophene Embedded Cellulose Paper for Enhanced Photothermal Water Evaporation and Prompt Bacterial Killing.

Solar-driven photothermal water evaporation is considered an elegant and sustainable technology for freshwater production. The existing systems, however, often suffer from poor stability and biofouling issues, which severely hamper their prospects in practical applications. Conventionally, photothermal materials are deposited on the membrane supports via vacuum-assisted filtration or dip-coating methods. Nevertheless, the weak inherent material-membrane interactions frequently lead to poor durability, and the photothermal material layer can be easily peeled off from the hosting substrates or partially dissolved when immersed in water. In the present article, the discovery of the incorporation of borophene into cellulose nanofibers (CNF), enabling excellent environmental stability with a high light-to-heat conversion efficiency of 91.5% and water evaporation rate of 1.45 kg m-2 h-1 under simulated sunlight is reported. It is also demonstrated that borophene papers can be employed as an excellent active photothermal material for eliminating almost 100% of both gram-positive and gram-negative bacteria within 20 min under three sun irradiations. The result opens a new direction for the design of borophene-based papers with unique photothermal properties which can be used for the effective treatment of a wide range of wastewaters.

Emerging Trends of Carbon-Based Quantum Dots: Nanoarchitectonics and Applications.

Carbon-based quantum dots (QDs) have emerged as a fascinating class of advanced materials with a unique combination of optoelectronic, biocompatible, and catalytic characteristics, apt for a plethora of applications ranging from electronic to photoelectrochemical devices. Recent research works have established carbon-based QDs for those frontline applications through improvements in materials design, processing, and device stability. This review broadly presents the recent progress in the synthesis of carbon-based QDs, including carbon QDs, graphene QDs, graphitic carbon nitride QDs and their heterostructures, as well as their salient applications. The synthesis methods of carbon-based QDs are first introduced, followed by an extensive discussion of the dependence of the device performance on the intrinsic properties and nanostructures of carbon-based QDs, aiming to present the general strategies for device designing with optimal performance. Furthermore, diverse applications of carbon-based QDs are presented, with an emphasis on the relationship between band alignment, charge transfer, and performance improvement. Among the applications discussed in this review, much focus is given to photo and electrocatalytic, energy storage and conversion, and bioapplications, which pose a grand challenge for rational materials and device designs. Finally, a summary is presented, and existing challenges and future directions are elaborated.

Advanced nanomaterials for highly efficient CO2 photoreduction and photocatalytic hydrogen evolution.

At present, CO2 photoreduction to value-added chemicals/fuels and photocatalytic hydrogen generation by water splitting are the most promising reactions to fix two main issues simultaneously, rising CO2 levels and never-lasting energy demand. CO2, a major contributor to greenhouse gases (GHGs) with about 65% of the total emission, is known to cause adverse effects like global temperature change, ocean acidification, greenhouse effects, etc. The idea of CO2 capture and its conversion to hydrocarbons can control the further rise of CO2 levels and help in producing alternative fuels that have several further applications. On the other hand, hydrogen being a zero-emission fuel is considered as a clean and sustainable form of energy that holds great promise for various industrial applications. The current review focuses on the discussion of the recent progress made in designing efficient photocatalytic materials for CO2 photoreduction and hydrogen evolution reaction (HER). The scope of the current study is limited to the TiO2 and non-TiO2 based advanced nanomaterials (i.e. metal chalcogenides, MOFs, carbon nitrides, single-atom catalysts, and low-dimensional nanomaterials). In detail, the influence of important factors that affect the performance of these photocatalysts towards CO2 photoreduction and HER is reviewed. Special attention is also given in this review to provide a brief account of CO2 adsorption modes on the catalyst surface and its subsequent reduction pathways/product selectivity. Finally, the review is concluded with additional outlooks regarding upcoming research on promising nanomaterials and reactor design strategies for increasing the efficiency of the photoreactions.